Epoxy resin compositions and premolded semiconductor packages

ABSTRACT

In an epoxy resin composition comprising an epoxy resin, a curing agent, and an inorganic filler, the filler is porous silica having a specific surface area of 6-200 m 2 /g, a true specific gravity of 2.0-2.2, and a mean particle size of 2-50 μm. The epoxy resin composition is readily moldable, has a low moisture permeability and reliability in the cured state, and is suitable for forming a premolded hollow semiconductor package.

[0001] This invention relates to epoxy resin compositions which areeasily moldable, have a low moisture permeability and reliability in thecured state, and are suitable for encapsulating semiconductor chips andespecially as premolded hollow semiconductor packages. It also relatesto premolded hollow semiconductor packages encapsulated with the epoxyresin compositions in the cured state.

BACKGROUND OF THE INVENTION

[0002] In the electrical and electronic fields, epoxy resins featuringmechanical strength, moisture resistance and moldability find a varietyof applications as insulating materials, laminates, adhesives andsemiconductor encapsulants.

[0003] As opposed to essentially moisture impermeable metals andceramics, epoxy resins classified as thermosetting resins have acoefficient of moisture diffusion. Upon exposure to humid conditions,epoxy resins absorb moisture and allow moisture to permeatetherethrough. The moisture permeability of thermosetting resins oftenbecomes a problem when they are used in the application requiringhermetic and water-proof seals, for example, in precision machines suchas watches and electronic calculators, and electronic parts such assemiconductor packages, especially solid state imaging device (generallyknown as CCD) hollow packages and quartz oscillator hollow packages. Forexample, resin packages of CCD slowly absorb moisture when exposed to ahot humid environment for an extended period of time, though not indirect contact with water. If moisture is introduced into the hermeticspace in excess of the saturated steam amount determined from thesaturated water vapor pressure, moisture condenses. The device becomesinoperable by dew condensation.

[0004] An improvement in moisture permeability has long been desired forprior art epoxy resin compositions comprising an epoxy resin, a curingagent and an inorganic filler for use in hollow packages. One knownmeans is to add an inorganic desiccant to the epoxy resin composition sothat the desiccant adsorbs moisture permeating through the cured item,preventing moisture from entering the hollow interior.

[0005] JP-A 8-157694 of the same assignee as the present inventiondiscloses an epoxy resin composition comprising at least 10 parts byweight of an inorganic desiccant per 100 parts by weight of an epoxyresin and a curing agent combined. Specifically, using AMT silica byMizusawa Chemical K.K. as the inorganic desiccant, the composition isrendered low moisture permeable.

[0006] AMT silica, however, has a low true specific gravity and containsa relatively large amount of ionic impurities since it is porous silicaobtained by sintering zeolite. The low true specific gravity means thata certain weight of silica added accounts for a larger volume so that anincreased amount of silica can obstruct flow. The large amount of ionicimpurities interfere with the curing function of the curing catalyst sothat cure may become short, resulting in drops of hot strength and bondstrength.

[0007] JP 2,750,254 (JPA 6-232292) discloses a semiconductor packagecomprising an insulating substrate containing 0.1 to 50% by weight of adesiccant. The amount of desiccant added to an epoxy resin compositionshould preferably be increased since a small amount of desiccant doesnot fully adsorb moisture penetrating through the cured item.Illustratively, in a moisture permeation reliability test, a packagesample containing a small amount of desiccant allows moisture to reachthe cavity so that moisture may condense on the glass lid. This drawbackcan be eliminated by increasing the amount of desiccant. However, sinceconventional desiccants are poorly compatible with epoxy resins andcuring agents, they exacerbate the flow particularly when added in largeamounts. The epoxy resin composition with retarded flow can cause suchdefects as short shots and voids when molded by a transfer moldingmachine, and is thus unsuitable for semiconductor encapsulatingpurposes.

[0008] An object of the invention is to provide an epoxy resincomposition which is flowable and easily moldable and cures into aproduct having a low moisture permeability, and a premolded hollowsemiconductor package encapsulated with the epoxy resin composition inthe cured state.

SUMMARY OF THE INVENTION

[0009] We have found that an epoxy resin composition comprising an epoxyresin, a curing agent, and an inorganic filler flows smoothly and iseasily moldable when the filler is porous silica having a specificsurface area of 6 to 200 m²/g, a true specific gravity of 2.0 to 2.2,and a mean particle size of 2 to 50 μm. The composition cures into aproduct of quality having a low moisture permeability. In summary, thecomposition is smoothly flowable and readily bondable and curable into aproduct having minimized moisture permeation. The composition is thussuited for forming premolded hollow semiconductor packages.

[0010] Accordingly the invention provides an epoxy resin compositioncomprising an epoxy resin, a curing agent, and an inorganic filler inthe form of porous silica having a specific surface area of 6 to 200m²/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of2 to 50 μm. In some preferred embodiments, the porous silica has beenprepared by forming a silica gel having a weight average particle sizeof up to 50 μm by a sol-gel process, and firing the silica gel at atemperature of 700 to 1,200° C.; the porous silica has a moisture pickupof at least 0.3% by weight when kept at 25° C. and RH 70% for 24 hours;the porous silica contains up to 1 ppm of each of alkali and alkalineearth metals. The porous silica preferably accounts for 40 to 90% byweight, more preferably at least 55% by weight of the entire epoxy resincomposition.

[0011] The invention also provides a premolded hollow semiconductorpackage encapsulated with a cured product of an epoxy resin compositioncomprising an epoxy resin, a curing agent, and an inorganic fillerincluding a porous silica having a specific surface area of 6 to 200m²/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of2 to 50 μm.

BRIEF DESCRIPTION OF THE DRAWING

[0012] The only FIGURE, FIG. 1 is a schematic cross-sectional view of apremolded hollow semiconductor package molded in Examples.

DESCRIPTION OF THE PREFERRED EMBODIMENT

[0013] The epoxy resin composition according to the invention containsan epoxy resin, a curing agent, and an inorganic filler. The epoxy resinused herein is not limited in molecular structure and molecular weightas long as it has at least two epoxy groups in a molecule and can becured with curing agents to be described later. A proper choice may bemade among conventional well-known epoxy resins. Examples of usefulepoxy resins include bisphenol type epoxy resins such as bisphenol Atype epoxy resins and bisphenol F type epoxy resins, novolak type epoxyresins such as phenol novolak type epoxy resins and cresol novolak typeepoxy resins, triphenolalkane type epoxy resins such as triphenolmethanetype epoxy resins and triphenolpropane type epoxy resins and polymersthereof, epoxy resins having a biphenyl skeleton, epoxy resins having anaphthalene skeleton, dicyclopentadiene-phenol novolak resins,phenolaralkyl type epoxy resins, glycidyl ester type epoxy resins,alicyclic epoxy resins, heterocyclic epoxy resins, and halogenated epoxyresins. Several preferred epoxy resins are illustrated by the followingformulas although the epoxy resin is not limited thereto.

[0014] Herein, G is glycidyl, Me is methyl, and n is an integer of 0 to10, and preferably 0 to 5.

[0015] The curing agent is not critical and may be any of phenoliccompounds, amine compounds and acid anhydrides commonly used for thecuring of conventional epoxy resins. Of these, phenolic resins having atleast two phenolic hydroxyl groups per molecule are preferred. Exemplarycuring agents include bisphenol type resins such as bisphenol A typeresins and bisphenol F type resins; novolak-type phenolic resins such asphenolic novolak resins and cresol novolak resins; triphenolalkaneresins such as triphenolmethane resins and triphenolpropane resins;resole type phenolic resins, phenol aralkyl resins, biphenyl typephenolic resins, naphthalene type phenolic resins, and cyclopentadienetype phenolic resins. These curing agents may be used alone or inadmixture of two or more. Several preferred, non-limiting examples ofthe curing agent are given below.

[0016] Herein, m is an integer of 0 to 10 and preferably 0 to 5.

[0017] The curing agent is blended in an effective amount to cause theepoxy resin to cure. When a phenolic resin is used as the curing agent,it is preferably blended in an epoxy resin in such amounts that 0.5 to1.6 mol, more preferably 0.6 to 1.4 mol of phenolic hydroxyl groups areavailable per mol of epoxy groups. Less than 0.5 mol of hydroxyl groupshave a possibility that more epoxy groups polymerize alone(homo-polymerization), resulting in a lower glass transitiontemperature. More than 1.6 mol means an excess of phenolic hydroxylgroups which may lower reactivity, resulting in a lower crosslinkingdensity and insufficient strength.

[0018] The porous silica used herein as the inorganic filler should havea specific surface area of 6 to 200 m²/g as expressed in BET specificsurface by the nitrogen adsorption method, a true specific gravity of2.0 to 2.2, and a mean particle size of 2 to 50 μm. It is noted that themean particle size as used herein can be determined, for example, as theweight average (or median diameter) in the particle size distribution asmeasured by the laser light diffraction method.

[0019] More illustratively, the porous silica has a specific surfacearea of 6 to 200 m²/g and preferably 20 to 150 m²/g. Silica with aspecific surface of less than 6 m²/g has a poor water absorbing capacitywhereas a specific surface of more than 200 m²/g adversely affects theflow. The porous silica has a true specific gravity of 2.0 to 2.2.Silica with a true specific gravity of less than 2.0 has an insufficientdegree of sintering and is less wettable to the epoxy resin. A truespecific gravity of more than 2.2 indicates mixing of crystallinesilica, which is outside the scope of porous silica which is amorphous.Additionally the porous silica has a mean particle size of 2 to 50 μmand preferably 4 to 20 μm. Outside this range, there can arise someproblems including retarded flow and burr formation.

[0020] In the porous silica, the content of each of alkali metals suchas Na and K and alkaline earth metals such as Mg and Ca shouldpreferably be 1 ppm or lower. Most preferably the total content ofalkali and alkaline earth metals is 1 ppm or lower. A higher content ofsuch ionic impurities can reduce the activity of the curing catalyst,resulting in undercure. In a composition having a large amount of poroussilica added, this tendency becomes outstanding if the content of ionicimpurities is high.

[0021] Also preferably, the porous silica itself has a water absorbingcapacity corresponding to a moisture pickup of at least 0.3%, morepreferably at least 0.4%, and most preferably at least 1.0% by weightwhen kept at 25° C. and RH 70% for 24 hours. If the moisture pickup ofporous silica is less than 0.3% by weight, the composition filledtherewith may have an insufficient water absorbing capacity.

[0022] Further preferably the porous silica has a pore volume of 0.05 to10 ml/g, more preferably of 0.1 to 1.0 ml/g and a pore diameter of 3 to100 Å.

[0023] In one preferred embodiment, the porous silica is prepared byforming a silica gel having a weight average particle size of up to 50Am by a sol-gel process, and firing the silica gel at a temperature of700 to 1,200° C. The sol-gel process used herein may be any of themethods described in JP-B 7-98659, JP-A 62-283809 and JP-A 62-3011 bothcorresponding to U.S. Pat. No. 4,683,128, for example. Depending on itspreparation method, the porous silica takes the form of sphericalparticles or fragments. For example, spherical porous silica is obtainedby forcedly agitating an aqueous alkali metal silicate emulsion in thepresence of a surfactant, followed by water washing, drying, andsintering. Fragment porous silica is obtained by extruding an aqueousalkali metal silicate emulsion into a water-miscible organic solvent oracid solution through orifices, treating the resulting fibrous coagulumswith an acidic solution, washing them with water to extract impuritiesaway, followed by pulverization and sintering.

[0024] The preferred conditions under which the porous silica obtainedby the sol-gel process is fired include a temperature of about 700 to1,200° C., more preferably about 800 to 1,100° C. and a time of about 2to 16 hours, more preferably about 4 to 12 hours. If the firingtemperature is below 700° C. or the firing time is too short, silica issintered to an insufficient extent to be wettable to the epoxy resin andcuring agent, failing to provide smooth flow. If the firing temperatureis above 1,200° C. or the firing time is too long, the number of poreson the silica surface is reduced due to over-sintering so that thesilica may have a low water absorbing capacity.

[0025] As mentioned above, the porous silica used herein is in the formof spherical particles or fragments. Spherical particles are preferredwhen the composition flow is taken into account. Silica fragments arepreferred for the mechanical strength of the composition in the curedstate. Since spherical particles are superior to fragments with respectto the water absorbing capacity of porous silica, it is preferred forincreasing the water absorbing capacity to add spherical particles more.It is noted that the magnitude of water absorbing capacity depends onthe size of pores. The proportion of spherical particles and fragmentsis not critical although a weight ratio of fragments/spherical particlesin the range from 0/10 to 3/7 is preferred for a good balance of flowand strength. Particularly when a large amount of porous silica isadded, it is recommended to increase the proportion of sphericalparticles.

[0026] The amount of porous silica added is preferably 40 to 90%, morepreferably 50 to 90%, most preferably 55 to 80% by weight of the entireepoxy resin composition. If the amount of porous silica added is lessthan 40% by weight, the composition may sometimes have a poor capacityto trap externally penetrating water, failing to achieve the desired lowmoisture permeability. If the amount of porous silica added is greaterthan 90% by weight, the composition may become less flowable anddifficult to mold.

[0027] While it is essential that the porous silica be used as theinorganic filler, other inorganic fillers may be additionally blended inthe epoxy resin composition of the invention. Such other inorganicfillers include fused silica as milled in a ball mill, spherical silicaobtained by flame fusion, crystalline silica, fumed silica, precipitatedsilica, alumina, boron nitride, aluminum nitride, silicon nitride,magnesia, and magnesium silicate. Preferably, the other inorganicfiller, if any, is used in such amounts that the total of inorganicfillers (inclusive of the inventive porous silica) may be 100 to 1,000parts by weight per 100 parts by weight of the epoxy resin and curingagent combined. If the total amount is less than 100 parts, thecomposition may have a higher coefficient of expansion. If the totalamount is more than 1,000 parts, the composition may become too viscousto mold. More preferably the total amount is 200 to 900 parts by weight.

[0028] For enhancing the bond strength of the inorganic filler to theresin, the inorganic filler is preferably surface treated beforehandwith coupling agents such as silane and titanate coupling agents.Preferred coupling agents are silane coupling agents in the form ofalkoxysilanes having alkyl groups substituted with such functionalgroups as epoxy, amino and mercapto groups, including epoxy silanes suchas γ-glycidoxypropyltrimethoxy-silane,γ-glycidoxypropylmethyldiethoxysilane, andβ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such asN-β-(aminoethyl)-γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, andN-phenyl-γ-aminopropyltrimethoxysilane; and mercaptosilanes such asγ-mercaptosilanes. No particular limitation is imposed on the amount ofcoupling agent used for surface treatment or the method of surfacetreatment.

[0029] In the inventive composition, conventional well-known siliconerubber and gel in powder form, silicone-modified epoxy resins,silicone-modified phenolic resins, and thermoplastic resins such asmethyl methacrylate-butadiene-styrene copolymers may be added asstress-relieving agents and adhesives.

[0030] In the practice of this invention, a curing accelerator ispreferably used for promoting the curing reaction between the epoxyresin and the curing agent. The curing accelerator may be any suitablesubstance that promotes the curing reaction. Illustrative, non-limitingexamples of curing accelerators that may be used include organicphosphorus compounds such as triphenylphosphine, tributylphosphine,tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine,triphenylphosphine triphenylborate, and tetraphenylphosphinetetraphenylborate; tertiary amine compounds such as triethylamine,benzyldimethylamine, a-methylbenzyldimethylamine, and1,8-diazabicyclo[5.4.0]-undecene-7; and imidazole compounds such as2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole. Anappropriate amount of the curing accelerator is about 0.01 to 10 partsby weight per 100 parts by weight of the epoxy resin and curing agent(e.g., phenolic resin) combined.

[0031] The epoxy resin composition may further include variousadditives, if necessary. Illustrative examples include coupling agentssuch as silane, titanium and aluminum coupling agents; colorants such ascarbon black; parting agents such as natural wax; wetting modifiers suchas fluorochemical surfactants and silicone oil; and halogen trappingagents.

[0032] The epoxy resin composition may be prepared by uniformly mixingthe essential and optional ingredients in a high-speed mixer or otherappropriate apparatus, and fully milling the mixture in a roll mill orcontinuous kneader. The desired milling temperature is about 50 to 120°C. After milling, the compound is sheeted, cooled and ground. Theresulting epoxy resin composition is useful as a general moldingmaterial and especially a semiconductor encapsulant.

[0033] The epoxy resin composition of the invention can be effectivelyused for encapsulating various types of semiconductor devices, andespecially for forming premolded hollow packages. The method ofencapsulation most commonly used is low-pressure transfer molding. Theepoxy resin composition is preferably molded at a temperature of about150 to 180° C. for a period of about 30 to 180 seconds, followed bypostcuring at about 150 to 180° C. for about 2 to 16 hours.

[0034] In the premolded hollow semiconductor package of the presentinvention, the package is encapsulated with a cured product of an epoxyresin composition comprising an epoxy resin, a curing agent, and aninorganic filler. The inorganic filler includes a porous silica having aspecific surface area of 6 to 200 m²/g, a true specific gravity of 2.0to 2.2, and a mean particle size of 2 to 50 μm, as described above. Theamount of the porous silica in the cured product or the entire epoxyresin composition is described above and preferably at least 55% byweight.

EXAMPLE

[0035] Examples of the invention are given below by way of illustrationand not by way of limitation. All parts are by weight.

Examples 1-10 and Comparative Examples 1-4

[0036] Semiconductor-encapsulating epoxy resin compositions wereprepared by mixing the porous silica shown in Table 1 with theingredients shown in Tables 2 and 3, and uniformly melt milling themixture in a hot two-roll mill, followed by cooling and grinding.

[0037] These epoxy resin compositions were examined for variousproperties by the following tests (1) to (9). The results are also shownin Tables 2 and 3.

[0038] (1) Spiral Flow:

[0039] The spiral flow was measured by molding the composition at 175°C. and 6.9 N/mm² for 120 seconds in a mold in accordance with EMMIstandards.

[0040] (2) Gel time

[0041] The gel time was measured as the time until the epoxy resincomposition gelled on a hot plate at 175° C.

[0042] (3) Melt viscosity

[0043] The melt viscosity was measured at 175° C. under a load of 10 kgwith a constant-load orifice-type flow testing apparatus of the kindknown in Japan as a Koka-type flow tester (Shimadzu Mfg. K.K.).

[0044] (4) Hardness as molded

[0045] According to JIS K6911, a rod measuring 100×10×4 mm was molded at175° C. and 6.9 N/mm² for 120 seconds. The hardness when hot wasmeasured with a Barcol Impressor.

[0046] (5) Flexural strength

[0047] According to JIS K6911, a rod measuring 100×10×4 mm was molded at175° C. and 6.9 N/mm² for 120 seconds and cured at 180° C. for 4 hoursbefore it was measured for flexural strength.

[0048] (6) Adhesion

[0049] A shear bond strength test piece was prepared by molding thecomposition over a frame of Alloy 42 at 175° C. and 6.9 N/mm² for 120seconds and curing at 180° C. for 4 hours. A bonding force was measured.The bond area between the frame and the resin was 10 mm².

[0050] (7) Moisture pickup

[0051] A disc having a diameter of 50 mm and a thickness of 3 mm wasmolded at 175° C. and 6.9 N/mm² for 120 seconds and cured at 180° C. for4 hours. The disc was held at 85° C. and RH 85% for 48 hours before theamount of water absorbed was measured.

[0052] (8) Thermal conductivity

[0053] A disc having a diameter of 50 mm and a thickness of 3 mm wasmolded at 175° C. and 6.9 N/mm² for 120 seconds and cured at 180° C. for4 hours. Thermal conductivity was measured in accordance with ASTM E1530 using ANTAR 2021.

[0054] (9) Hermetic test

[0055] A premolded package 1 of hollow box shape as shown in FIG. 1 wasprepared by molding the epoxy resin composition over a lead frame 2(including inner and outer leads 2 a and 2 b) at 175° C. and 6.9 N/mm²for 120 seconds and postcuring at 180° C. for 4 hours. A transparentglass shield 4 was joined to the top of the package 1 with an epoxyresin adhesive 3, completing the hollow package. Note that asemiconductor chip 5 and metal bonding wires 6 are on the lead frame 2.

[0056] This package was subjected to a thermal cycling test. The testprocedure included four steps of (1) holding in an atmosphere of 121°C./RH 100%/2 atm. for 4 hours, (2) holding at room temperature (25° C.)for 30 minutes, (3) placing the glass shield in contact with a hot plateat 100° C. for 10 seconds, and (4) placing the glass shield in contactwith an iron plate at room temperature for 7 seconds. This was repeatedfour cycles. It was observed whether or not the glass shield was cloudedby dew condensation. The sample was rated “NG” when dew condensationoccurred in the first cycle, and “1,” “2,” “3” and “4” when it clearedthe first, second, third and fourth cycle, respectively. TABLE 1 Used inUsed in Example Comparative Example Porous silica 1 2 3 4 5 AMT #2000Shape spherical spherical spherical fragment spherical — Sintering temp.(° C.) 800 900 980 1.100 1.250 — Mean particle size 8.7 9.6 16 31 15 2(μm) Specific surface (m²/g) 144 75 21 35 4 125 Moisture pickup 15 7.43.4 0.48 0.2 17 @ 25° C./RH 70%/24 hr (wt %) Extracted water pH 4.4 4.44.5 4.4 4.5 5.8 True specific gravity 2.1 2.2 2.2 2.2 2.2 1.9 (g/cm³)Specific gravity 0.95 1.00 1.00 1.00 1.00 0.86 ratio to specific gravity2.20 fused silica Al content (ppm) 1.0 1.2 1.0 0.9 0.9 1.100 Fe content(ppm) 2.1 2.0 2.3 2.0 2.3 25 Total content of <1  <1  <1  <1  <1  243alkali metal (Na and K) (ppm) Total content of <1  <1  <1  <1  <1  364alkali earth metal (Mg and Ca) (ppm) U content (ppb) 0.1 0.1 0.1 0.1 0.11.4

[0057] Note that porous silica Nos. 1 to 5 were respectively prepared byforming a silica gel having a weight average particle size of 9.2 μm, 10μm, 17 μm, 32 μm and 13 μm by the sol-gel process, and firing the silicagel at the indicated temperature for 8 hours. The contents of Al, Fe,Na, Ca, Mg and K were measured by ICP, and the content of U was measuredby fluorescent x-ray analysis. Porous silica Nos. 1 to 4 were used inExamples and porous silica No. 5 and AMT #2000 (zeolite by MizusawaChemical K.K.) were used in Comparative Examples. TABLE 2 ExampleComparative Example Formulation (pbw) 1 2 3 4 5 1 2 Novolak type epoxyresin¹⁾ 59.1 59.1 59.1 59.1 59.1 59.1 59.1 Curing agent³⁾ 35.4 35.4 35.435.4 35.4 35.4 35.4 Brominated epoxy resin⁵⁾ 5 5 5 5 5 5 5 Silanecoupling agent⁶⁾ 1.5 1.5 1.5 1.5 1.5 1.5 1.5 Hoechst Wax E 1.5 1.5 1.51.5 1.5 1.5 1.5 Triphenylphosphine 1.3 1.3 1.3 1.3 1.3 1.3 1.3 Sb₂O₃ 5 55 5 5 5 5 Porous silica No. 1 346 — — 277 277 — — Porous silica No. 2 —346 — — — — — Porous silica No. 3 — — 346 — — — — Porous silica No. 4 —— — 69 — — — Porous silica No. 5 — — — — — 346 — AMT #2000 — — — — — —346 Spherical silica⁷⁾ 18 18 18 18 18 18 18 Micro-spherical silica⁸⁾ 104104 104 104 104 104 104 Micro-spherical silica⁹⁾ 52 52 52 52 52 52 52Spherical alumina¹⁰⁾ — — — — 69 — — Porous silica content (wt %) 55 5555 55 44 55 — Spiral flow (cm) 95 105 110 95 96 106 32 Gel time (sec) 1616 15 16 15 16 20 Melt viscosity (Pa · s) 20 18 18 20 16 18 500 Moldedhardness 85 87 85 85 86 87 75 Flexural strength (N/mm²) 142 142 132 142142 142 108 Bonding force (kg) 4.2 4.1 3.9 4.3 4.0 3.8 0.2 Moisturepickup (wt %) 3.0 2.3 2.1 1.8 1.8 1.0 3.0 Thermal conductivity (W/mK)0.9 0.9 0.9 0.9 1.4 0.9 0.9 Hermetic test 4 4 4 4 3 NG 1

[0058] TABLE 3 Example Comparative Example Formulation (pbw) 6 7 8 9 103 Novolac type epoxy resin¹⁾ 59.1 59.1 59.1 59.1 — 59.1 Biphenyl typeepoxy resin²⁾ — — — — 45.6 — Curing agent³⁾ 35.4 35.4 35.4 35.4 — 35.4Curing agent⁴⁾ — — — — 47.0 — Brominated epoxy resin⁵⁾ 5 5 5 5 5 5Silane coupling agent⁶⁾ 1.5 1.5 1.5 1.5 1.5 1.5 Hoechst Wax E 1.5 1.51.5 1.5 1.5 1.5 Triphenylphosphine 1.3 1.3 1.3 1.3 1.3 1.3 Sb₂O₃ 5 5 5 55 5 Porous silica No. 1 63 315 378 362 472.5 — Spherical silica⁷⁾ 301 49— 56 73.5 364 Micro-spherical silica⁸⁾ 104 104 90 120 156 104Micro-spherical silica⁹⁾ 52 52 52 60 78 52 Porous silica content (wt %)10 50 60 51 53 — Spiral flow (cm) 115 112 90 95 100 120 Gel time (sec)16 16 16 16 16 16 Melt viscosity (Pa · s) 19 18 21 16 18 14 Moldedhardness 85 86 87 86 85 86 Flexural strength (N/mm²⁾ 142 137 147 147 147137 Bonding force (kg) 4.1 3.9 3.9 4.2 4.0 2.8 Moisture pickup (wt %)0.7 3.1 3.3 2.6 2.2 0.4 Hermetic test 1 3 4 3 3 NG

[0059] The epoxy resin compositions within the scope of the inventionand the semiconductor packages encapsulated therewith exhibit excellentproperties as demonstrated by the above Examples. It is seen from Table2 that when silica having a smaller specific surface area and a smallermoisture pickup is used, the hollow package does not provide asatisfactory hermetic seal in the hermetic test. When conventionalporous silica (zeolite) is used, flow, cure, adhesion and hermetic sealare unsatisfactory under the influence of impurities. It is seen fromTable 3 that when porous silica within the scope of the invention isused, but in a smaller amount, the results of the hermetic test areunsatisfactory. The hermetic level rises as the amount of porous silicaadded increases.

[0060] There has been described a porous silica-loaded epoxy resincomposition which is easy to mold and cures into a part having lowmoisture permeability and high reliability.

[0061] Japanese Patent Application No. 11-342946 is incorporated hereinby reference.

[0062] Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

What is claimed is:
 1. A premolded hollow semiconductor packageencapsulated with a cured product of an epoxy resin compositioncomprising an epoxy resin, a curing agent, and an inorganic fillerincluding a porous silica having a specific surface area of 6 to 200m²/g, a true specific gravity of 2.0 to 2.2, and a mean particle size of2 to 50 μm.
 2. The premolded hollow semiconductor package of claim 1,wherein the porous silica accounts for at least 55% by weight of theentire epoxy resin composition.
 3. The premolded hollow semiconductorpackage of claim 1, wherein the porous silica has been prepared byforming a silica gel having a weight average particle size of up to 50μm by a sol-gel process, and firing the silica gel at a temperature of700 to 1,200° C.
 4. The premolded hollow semiconductor package of claim1, wherein the porous silica has a moisture pickup of at least 0.3% byweight when kept at 25° C. and RH 70% for 24 hours.
 5. The premoldedhollow semiconductor package of claim 1, wherein the porous silicacontains up to 1 ppm of each of alkali and alkaline earth metals.
 6. Thepremolded hollow semiconductor package of claim 1, wherein the epoxyresin is illustrated by one of the following formulas:

wherein G is glycidyl, Me is methyl, and n is an integer of 0 to
 10. 7.The premolded hollow semiconductor package of claim 1, wherein thecuring agent is illustrated by one of the following formulas:

wherein m is an integer of 0 to
 10. 8. The premolded hollowsemiconductor package of claim 1, wherein the specific surface area is20 to 150 m²/g.
 9. The premolded hollow semiconductor package of claim1, wherein the mean particle size is 4 to 20 μm.
 10. The premoldedhollow semiconductor package of claim 1 or 2, wherein the porous silicaaccounts for 55 to 90% by weight of the entire epoxy resin composition.11. The premolded hollow semiconductor package of claim 1, wherein theporous silica has a pore volume of 0.05 to 10 ml/g and a pore diameterof 3 to 100 Å.
 12. The premolded hollow semiconductor package of claim3, wherein the firing of the silica gel is at a temperature of 800 to1,100° C.
 13. The premolded hollow semiconductor package of claim 1,wherein the epoxy resin composition further comprises at least one ofthe following: a coupling agent, a colorant, a parting agent, a wettingmodifier, and a halogen trapping agent.